The dehydration process in the dl-phenyl­glycinium tri­fluoro­methane­sulfonate monohydrate crystal revealed by XRD, vibrational and DSC studies

Wołoszyn, Ł.; Ilczyszyn, M.M.; Kinzhybalo, V.

doi:10.1107/S2053229619014402

The dehydration process in the DL-phenylglycinium trifluoromethanesulfonate monohydrate crystal revealed by XRD, vibrational and DSC studies

Ł. Wołoszyn, M. M. Ilczyszyn and V. Kinzhybalo

Thermal analysis, X-ray diffraction and temperature-dependent IR spectroscopy were used to study the dehydration process of crystalline DL-phenylglycinium trifluoromethanesulfonate monohydrate (PGTFH), C₈H₁₀NO₂⁺·CF₃SO₃⁻·H₂O. PGTFH dehydrates in one step centred at 353 K and crystallizes in the monoclinic space group C2/c, whereas the anhydrous compound (PGTF) crystallizes in the triclinic space group P $\overline{1}$ . The dehydration process in PGTFH is preceded by a weakening of both the noncovalent aromatic–aromatic interactions and the packing contacts. This process is accompanied by the breakage of medium-strength O—H

O hydrogen bonds between ions inside layers and a reorganization of the ions within the layers. This reorganization results in the formation of two different ion pairs (DL-phenylglycinium trifluoromethanesulfonate) and the formation of a new hydrogen-bond network. The dehydration process does not destroy the nature of the crystal structure. Both crystals, i.e. hydrated and anhydrous, have a layered structure, although the layers of each crystal are arranged somewhat differently.

Keywords: phenylglycinium; trifluoromethanesulfonate; dehydration; crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229619014402/jx3047sup1.cif Contains datablocks ptfh_abs_twin1_hklf4, ptf_1, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229619014402/jx3047ptfh_abs_twin1_hklf4sup2.hkl Contains datablock ptfh_abs_twin1_hklf4
	Chemdraw file https://doi.org/10.1107/S2053229619014402/jx3047ptfh_abs_twin1_hklf4sup4.cdx Supplementary material
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229619014402/jx3047ptf_1sup3.hkl Contains datablock ptf_1
	Chemdraw file https://doi.org/10.1107/S2053229619014402/jx3047ptf_1sup5.cdx Supplementary material
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229619014402/jx3047sup6.pdf Additional tables, information and figures

CCDC references: 1902197; 1902198

Computing details top

For both structures, data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

DL-Phenylglycinium trifluoromethanesulfonate monohydrate (ptfh_abs_twin1_hklf4) top

Crystal data top

C₈H₁₀NO₂⁺·CF₃O₃S⁻·H₂O	F(000) = 1312
M_r = 319.26	D_x = 1.589 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.804 (5) Å	Cell parameters from 3549 reflections
b = 5.792 (2) Å	θ = 3.7–29.0°
c = 24.523 (6) Å	µ = 0.30 mm⁻¹
β = 92.57 (3)°	T = 100 K
V = 2668.2 (13) Å³	Plate, colourless
Z = 8	0.42 × 0.37 × 0.08 mm

Data collection top

Rigaku Xcalibur Atlas diffractometer	3085 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2316 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.072
Detector resolution: 10.6249 pixels mm^-1	θ_max = 29.4°, θ_min = 3.7°
ω scans	h = −24→24
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2018)	k = −5→7
T_min = 0.891, T_max = 0.974	l = −32→28
8083 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.153	w = 1/[σ²(F_o²) + (0.0884P)² + 2.4562P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3085 reflections	Δρ_max = 0.52 e Å⁻³
191 parameters	Δρ_min = −0.53 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The single-crystal XRD measurements for hydrated form PGTFH and anhydrous form PGTF were performed on an Xcalibur CCD diffractometer (Mo Kα radiation, λ = 0.71073 nm). The crystallographic data for PGTFH were collected at 100 K. CrysAlis CCD and CrysAlis RED were used for data collection and reduction (Rigaku OD, 2015). The crystal structure was solved and refined using the SHELXT (Sheldrick, 2015a) and SHELXL (Sheldrick, 2015b) software packages. Non-hydrogen bonded atoms were refined with anisotropic displacement parameters.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1A	0.49397 (3)	0.20005 (11)	0.41586 (2)	0.01486 (18)
O1A	0.55588 (10)	0.0539 (3)	0.42069 (7)	0.0241 (4)
O2A	0.43939 (10)	0.1506 (3)	0.45376 (7)	0.0230 (4)
O3A	0.50941 (9)	0.4451 (3)	0.41086 (7)	0.0186 (4)
C1A	0.45288 (15)	0.1260 (5)	0.34933 (11)	0.0248 (6)
F1A	0.43419 (10)	−0.0963 (3)	0.34787 (6)	0.0343 (5)
F2A	0.39490 (11)	0.2523 (4)	0.33923 (8)	0.0467 (6)
F3A	0.49720 (11)	0.1635 (4)	0.30971 (7)	0.0443 (6)
O1B	0.28684 (9)	0.8192 (3)	0.41034 (7)	0.0192 (4)
H1B	0.325796	0.782411	0.426084	0.029*
O2B	0.26903 (9)	1.0031 (3)	0.48952 (7)	0.0170 (4)
C1B	0.24969 (13)	0.9442 (4)	0.44343 (9)	0.0137 (5)
C2B	0.17706 (12)	1.0075 (4)	0.41768 (9)	0.0145 (5)
H2B	0.149778	0.862043	0.410004	0.017*
N1B	0.13842 (11)	1.1464 (4)	0.45883 (8)	0.0148 (4)
H1BC	0.121974	1.050526	0.484829	0.018*
H1BB	0.101125	1.221370	0.441821	0.018*
H1BA	0.168759	1.251415	0.474764	0.018*
C3B	0.18124 (14)	1.1420 (5)	0.36488 (10)	0.0163 (5)
C4B	0.22151 (15)	1.3414 (5)	0.36345 (10)	0.0216 (6)
H4B	0.248452	1.389678	0.395110	0.026*
C5B	0.22272 (16)	1.4717 (5)	0.31577 (11)	0.0254 (6)
H5B	0.250175	1.609230	0.315000	0.030*
C6B	0.18404 (16)	1.4008 (5)	0.26972 (11)	0.0275 (6)
H6B	0.185179	1.489075	0.237117	0.033*
C7B	0.14350 (16)	1.2013 (6)	0.27080 (11)	0.0286 (7)
H7B	0.116787	1.153213	0.239005	0.034*
C8B	0.14190 (15)	1.0707 (5)	0.31863 (10)	0.0237 (6)
H8B	0.114061	0.934021	0.319512	0.028*
O1W	0.40477 (10)	0.6858 (4)	0.46303 (7)	0.0176 (4)
H1W	0.420 (2)	0.813 (8)	0.4692 (15)	0.045 (12)*
H2W	0.437 (3)	0.599 (8)	0.4450 (17)	0.069 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1A	0.0104 (3)	0.0164 (3)	0.0177 (3)	0.0006 (2)	−0.0001 (2)	−0.0003 (2)
O1A	0.0169 (10)	0.0214 (10)	0.0334 (10)	0.0068 (8)	−0.0046 (8)	−0.0016 (8)
O2A	0.0228 (11)	0.0204 (10)	0.0263 (10)	−0.0049 (8)	0.0088 (8)	−0.0023 (7)
O3A	0.0130 (9)	0.0178 (10)	0.0251 (9)	−0.0031 (7)	0.0011 (7)	0.0012 (7)
C1A	0.0200 (14)	0.0309 (16)	0.0232 (13)	−0.0044 (12)	−0.0030 (10)	0.0027 (11)
F1A	0.0406 (11)	0.0309 (10)	0.0310 (9)	−0.0151 (8)	−0.0031 (7)	−0.0077 (7)
F2A	0.0337 (11)	0.0524 (14)	0.0515 (11)	0.0037 (9)	−0.0268 (9)	0.0046 (9)
F3A	0.0516 (14)	0.0612 (15)	0.0208 (9)	−0.0245 (11)	0.0077 (8)	−0.0041 (8)
O1B	0.0086 (9)	0.0249 (11)	0.0241 (9)	0.0053 (7)	−0.0003 (7)	−0.0022 (7)
O2B	0.0127 (9)	0.0162 (10)	0.0218 (9)	0.0006 (7)	−0.0022 (6)	−0.0007 (7)
C1B	0.0086 (11)	0.0110 (12)	0.0217 (12)	−0.0011 (9)	0.0022 (8)	0.0010 (9)
C2B	0.0094 (12)	0.0157 (13)	0.0182 (12)	0.0002 (9)	−0.0007 (8)	−0.0017 (9)
N1B	0.0078 (10)	0.0173 (11)	0.0193 (10)	−0.0001 (8)	0.0002 (7)	−0.0011 (8)
C3B	0.0104 (11)	0.0188 (13)	0.0199 (12)	0.0025 (10)	0.0017 (9)	−0.0008 (9)
C4B	0.0191 (14)	0.0247 (15)	0.0211 (12)	−0.0013 (11)	0.0001 (10)	0.0007 (10)
C5B	0.0283 (16)	0.0220 (15)	0.0260 (14)	0.0000 (12)	0.0032 (11)	0.0023 (11)
C6B	0.0278 (16)	0.0315 (17)	0.0234 (14)	0.0088 (13)	0.0029 (11)	0.0078 (11)
C7B	0.0255 (15)	0.0392 (18)	0.0205 (13)	0.0005 (13)	−0.0041 (11)	0.0001 (12)
C8B	0.0177 (14)	0.0301 (17)	0.0231 (13)	−0.0038 (12)	−0.0019 (10)	−0.0005 (11)
O1W	0.0110 (9)	0.0171 (10)	0.0250 (9)	0.0027 (8)	0.0023 (7)	−0.0005 (7)

Geometric parameters (Å, º) top

S1A—O1A	1.440 (2)	N1B—H1BB	0.9100
S1A—O2A	1.4439 (19)	N1B—H1BA	0.9100
S1A—O3A	1.455 (2)	C3B—C4B	1.382 (4)
S1A—C1A	1.825 (3)	C3B—C8B	1.389 (4)
C1A—F1A	1.335 (3)	C4B—H4B	0.9500
C1A—F2A	1.327 (4)	C4B—C5B	1.393 (4)
C1A—F3A	1.326 (3)	C5B—H5B	0.9500
O1B—H1B	0.8400	C5B—C6B	1.378 (4)
O1B—C1B	1.312 (3)	C6B—H6B	0.9500
O2B—C1B	1.221 (3)	C6B—C7B	1.385 (5)
C1B—C2B	1.523 (3)	C7B—H7B	0.9500
C2B—H2B	1.0000	C7B—C8B	1.397 (4)
C2B—N1B	1.503 (3)	C8B—H8B	0.9500
C2B—C3B	1.516 (3)	O1W—H1W	0.80 (5)
N1B—H1BC	0.9100	O1W—H2W	0.91 (5)

O1A—S1A—O2A	115.19 (12)	C2B—N1B—H1BA	109.5
O1A—S1A—O3A	114.63 (11)	H1BC—N1B—H1BB	109.5
O1A—S1A—C1A	104.11 (13)	H1BC—N1B—H1BA	109.5
O2A—S1A—O3A	113.46 (11)	H1BB—N1B—H1BA	109.5
O2A—S1A—C1A	104.13 (12)	C4B—C3B—C2B	120.0 (2)
O3A—S1A—C1A	103.42 (12)	C4B—C3B—C8B	120.0 (2)
F1A—C1A—S1A	110.56 (18)	C8B—C3B—C2B	119.9 (2)
F2A—C1A—S1A	110.4 (2)	C3B—C4B—H4B	119.9
F2A—C1A—F1A	108.3 (2)	C3B—C4B—C5B	120.2 (2)
F3A—C1A—S1A	111.21 (19)	C5B—C4B—H4B	119.9
F3A—C1A—F1A	108.2 (2)	C4B—C5B—H5B	120.0
F3A—C1A—F2A	108.1 (2)	C6B—C5B—C4B	119.9 (3)
C1B—O1B—H1B	109.5	C6B—C5B—H5B	120.0
O1B—C1B—C2B	111.6 (2)	C5B—C6B—H6B	119.9
O2B—C1B—O1B	125.6 (2)	C5B—C6B—C7B	120.2 (3)
O2B—C1B—C2B	122.8 (2)	C7B—C6B—H6B	119.9
C1B—C2B—H2B	108.5	C6B—C7B—H7B	120.0
N1B—C2B—C1B	107.57 (18)	C6B—C7B—C8B	120.0 (3)
N1B—C2B—H2B	108.5	C8B—C7B—H7B	120.0
N1B—C2B—C3B	110.1 (2)	C3B—C8B—C7B	119.6 (3)
C3B—C2B—C1B	113.4 (2)	C3B—C8B—H8B	120.2
C3B—C2B—H2B	108.5	C7B—C8B—H8B	120.2
C2B—N1B—H1BC	109.5	H1W—O1W—H2W	110 (4)
C2B—N1B—H1BB	109.5

O1A—S1A—C1A—F1A	61.1 (2)	C1B—C2B—C3B—C4B	−53.8 (3)
O1A—S1A—C1A—F2A	−179.15 (19)	C1B—C2B—C3B—C8B	129.3 (3)
O1A—S1A—C1A—F3A	−59.1 (2)	C2B—C3B—C4B—C5B	−176.8 (2)
O2A—S1A—C1A—F1A	−60.0 (2)	C2B—C3B—C8B—C7B	177.1 (3)
O2A—S1A—C1A—F2A	59.8 (2)	N1B—C2B—C3B—C4B	66.8 (3)
O2A—S1A—C1A—F3A	179.8 (2)	N1B—C2B—C3B—C8B	−110.1 (3)
O3A—S1A—C1A—F1A	−178.83 (19)	C3B—C4B—C5B—C6B	−0.5 (4)
O3A—S1A—C1A—F2A	−59.0 (2)	C4B—C3B—C8B—C7B	0.2 (4)
O3A—S1A—C1A—F3A	61.0 (2)	C4B—C5B—C6B—C7B	0.5 (4)
O1B—C1B—C2B—N1B	179.1 (2)	C5B—C6B—C7B—C8B	−0.2 (5)
O1B—C1B—C2B—C3B	−58.9 (3)	C6B—C7B—C8B—C3B	−0.1 (5)
O2B—C1B—C2B—N1B	−0.1 (3)	C8B—C3B—C4B—C5B	0.1 (4)
O2B—C1B—C2B—C3B	121.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1B—H1B···O1W	0.84	1.79	2.632 (3)	175
C2B—H2B···O1Aⁱ	1.00	2.53	3.481 (3)	158
N1B—H1BC···O1Wⁱⁱ	0.91	1.95	2.859 (3)	172
N1B—H1BB···O1Aⁱⁱⁱ	0.91	2.16	2.954 (3)	145
N1B—H1BA···O2B^iv	0.91	2.02	2.925 (3)	177
O1W—H1W···O2A^v	0.80 (5)	2.03 (5)	2.781 (3)	156 (4)
O1W—H2W···O3A	0.91 (5)	1.86 (5)	2.771 (3)	174 (4)

Symmetry codes: (i) x−1/2, y+1/2, z; (ii) −x+1/2, −y+3/2, −z+1; (iii) x−1/2, y+3/2, z; (iv) −x+1/2, −y+5/2, −z+1; (v) x, y+1, z.

DL-Phenylglycinium trifluoromethanesulfonate (ptf_1) top

Crystal data top

C₈H₁₀NO₂⁺·CF₃O₃S⁻	Z = 4
M_r = 301.24	F(000) = 616
Triclinic, P1	D_x = 1.608 Mg m⁻³
a = 10.485 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.635 (4) Å	Cell parameters from 2218 reflections
c = 13.734 (5) Å	θ = 3.1–25.9°
α = 104.79 (3)°	µ = 0.31 mm⁻¹
β = 98.04 (3)°	T = 373 K
γ = 118.07 (3)°	Irregular
V = 1244.4 (9) Å³

Data collection top

Rigaku Xcalibur, Sapphire1, long nozzle diffractometer	6208 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2625 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.086
Detector resolution: 8.4350 pixels mm^-1	θ_max = 29.6°, θ_min = 3.2°
ω scans	h = −14→14
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018)	k = −14→12
T_min = 0.729, T_max = 1.000	l = −17→18
14080 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.092	H-atom parameters constrained
wR(F²) = 0.274	w = 1/[σ²(F_o²) + (0.0827P)² + 1.8829P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
6208 reflections	Δρ_max = 0.36 e Å⁻³
372 parameters	Δρ_min = −0.43 e Å⁻³
0 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1A1	0.10042 (17)	0.21499 (17)	0.87773 (12)	0.0458 (4)
O1A1	0.0000 (5)	0.0878 (5)	0.9018 (4)	0.0687 (13)
O2A1	0.1137 (6)	0.3569 (5)	0.9338 (3)	0.0644 (12)
O3A1	0.2388 (5)	0.2235 (6)	0.8783 (4)	0.0782 (15)
C1A1	0.0143 (9)	0.1714 (9)	0.7418 (5)	0.0668 (19)
F1A1	0.0891 (7)	0.2817 (7)	0.7109 (4)	0.130 (2)
F2A1	−0.1203 (6)	0.1570 (7)	0.7276 (4)	0.1218 (19)
F3A1	−0.0049 (8)	0.0489 (7)	0.6779 (4)	0.134 (2)
S1A2	0.55384 (18)	0.65876 (17)	0.84295 (12)	0.0486 (4)
O1A2	0.6600 (5)	0.6116 (5)	0.8498 (4)	0.0627 (14)	0.948 (5)
O2A2	0.6213 (7)	0.8183 (5)	0.8697 (4)	0.088 (2)	0.948 (5)
O3A2	0.4361 (6)	0.5851 (7)	0.8858 (4)	0.0863 (19)	0.948 (5)
O1X2	0.487 (9)	0.756 (9)	0.878 (6)	0.05 (2)*	0.052 (5)
O2X2	0.539 (7)	0.568 (7)	0.890 (5)	0.029 (16)*	0.052 (5)
O3X2	0.727 (7)	0.773 (7)	0.880 (4)	0.027 (15)*	0.052 (5)
C1A2	0.4592 (8)	0.5810 (8)	0.7032 (5)	0.0604 (17)
F1A2	0.3883 (8)	0.4312 (6)	0.6644 (4)	0.112 (2)	0.948 (5)
F2A2	0.5500 (6)	0.6274 (9)	0.6476 (4)	0.125 (3)	0.948 (5)
F3A2	0.3567 (6)	0.6142 (7)	0.6811 (4)	0.112 (2)	0.948 (5)
F1X2	0.493 (6)	0.699 (6)	0.669 (4)	0.030 (14)*	0.052 (5)
F2X2	0.322 (5)	0.470 (6)	0.663 (3)	0.019 (12)*	0.052 (5)
F3X2	0.527 (7)	0.519 (7)	0.667 (5)	0.039 (15)*	0.052 (5)
O1B1	−0.0017 (5)	0.5153 (5)	0.8687 (4)	0.0659 (13)
H1B1	0.041384	0.469028	0.874748	0.099*
O2B1	0.2195 (5)	0.7206 (5)	0.9728 (4)	0.0672 (13)
C1B1	0.0977 (7)	0.6632 (7)	0.9103 (5)	0.0443 (13)
C2B1	0.0403 (6)	0.7529 (6)	0.8722 (4)	0.0416 (13)
H2B1	−0.058393	0.722894	0.883974	0.050*
N1B1	0.1497 (5)	0.9189 (5)	0.9386 (3)	0.0451 (11)
H1BA	0.149324	0.935045	1.005373	0.054*
H1BB	0.122208	0.975498	0.914537	0.054*
H1BC	0.242549	0.944897	0.935250	0.054*
C3B1	0.0209 (6)	0.7258 (6)	0.7572 (4)	0.0433 (13)
C4B1	−0.1023 (8)	0.7115 (9)	0.6943 (5)	0.0688 (19)
H4B1	−0.175166	0.716222	0.723965	0.083*
C5B1	−0.1223 (10)	0.6905 (10)	0.5902 (6)	0.090 (3)
H5B1	−0.207807	0.680218	0.549464	0.108*
C6B1	−0.0166 (11)	0.6849 (9)	0.5468 (6)	0.084 (2)
H6B1	−0.028819	0.671165	0.475753	0.101*
C7B1	0.1093 (11)	0.6994 (10)	0.6074 (6)	0.088 (3)
H7B1	0.181030	0.693676	0.576751	0.106*
C8B1	0.1295 (8)	0.7223 (9)	0.7131 (5)	0.069 (2)
H8B1	0.216270	0.735391	0.754396	0.083*
O1B2	0.6019 (6)	0.0230 (6)	0.8074 (4)	0.0758 (14)
H1B2	0.582690	−0.047899	0.828059	0.114*
O2B2	0.4404 (5)	0.0472 (5)	0.8888 (4)	0.0602 (12)
C1B2	0.5346 (7)	0.0933 (7)	0.8460 (5)	0.0471 (14)
C2B2	0.5930 (7)	0.2413 (6)	0.8265 (4)	0.0435 (13)
H2B2	0.703706	0.293941	0.843800	0.052*
N1B2	0.5548 (6)	0.3384 (5)	0.8983 (4)	0.0485 (12)
H1BD	0.596853	0.355609	0.964950	0.058*
H1BE	0.454440	0.290863	0.884235	0.058*
H1BF	0.589893	0.427185	0.888913	0.058*
C3B2	0.5274 (7)	0.2092 (7)	0.7120 (4)	0.0457 (14)
C4B2	0.6236 (9)	0.2745 (9)	0.6572 (5)	0.070 (2)
H4B2	0.727454	0.339771	0.690657	0.084*
C5B2	0.5626 (12)	0.2411 (11)	0.5505 (7)	0.093 (3)
H5B2	0.626868	0.286125	0.513142	0.112*
C6B2	0.4133 (11)	0.1453 (10)	0.5003 (6)	0.084 (2)
H6B2	0.374751	0.122497	0.428673	0.101*
C7B2	0.3197 (10)	0.0825 (9)	0.5554 (6)	0.087 (3)
H7B2	0.216023	0.016921	0.521258	0.105*
C8B2	0.3753 (8)	0.1140 (8)	0.6602 (5)	0.070 (2)
H8B2	0.309090	0.070416	0.696895	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1A1	0.0514 (9)	0.0479 (9)	0.0497 (9)	0.0294 (8)	0.0193 (7)	0.0262 (7)
O1A1	0.087 (3)	0.051 (3)	0.077 (3)	0.031 (3)	0.041 (3)	0.041 (2)
O2A1	0.097 (4)	0.052 (3)	0.059 (3)	0.052 (3)	0.019 (3)	0.021 (2)
O3A1	0.065 (3)	0.118 (4)	0.082 (3)	0.064 (3)	0.028 (3)	0.048 (3)
C1A1	0.072 (5)	0.080 (5)	0.054 (4)	0.040 (4)	0.021 (4)	0.031 (4)
F1A1	0.149 (5)	0.144 (5)	0.083 (3)	0.048 (4)	0.030 (3)	0.083 (4)
F2A1	0.081 (3)	0.185 (6)	0.092 (4)	0.078 (4)	0.000 (3)	0.037 (4)
F3A1	0.210 (7)	0.133 (5)	0.058 (3)	0.115 (5)	0.008 (3)	0.002 (3)
S1A2	0.0564 (10)	0.0419 (9)	0.0478 (9)	0.0250 (8)	0.0125 (7)	0.0210 (7)
O1A2	0.073 (3)	0.073 (3)	0.062 (3)	0.049 (3)	0.015 (3)	0.034 (3)
O2A2	0.102 (5)	0.036 (3)	0.098 (4)	0.031 (3)	−0.016 (3)	0.019 (3)
O3A2	0.076 (4)	0.104 (5)	0.062 (3)	0.027 (3)	0.037 (3)	0.038 (3)
C1A2	0.070 (5)	0.063 (5)	0.063 (4)	0.045 (4)	0.022 (4)	0.021 (4)
F1A2	0.144 (6)	0.078 (4)	0.076 (3)	0.059 (4)	−0.010 (3)	−0.006 (3)
F2A2	0.103 (4)	0.228 (7)	0.073 (3)	0.085 (5)	0.044 (3)	0.093 (4)
F3A2	0.114 (4)	0.169 (6)	0.078 (3)	0.113 (4)	−0.002 (3)	0.022 (3)
O1B1	0.063 (3)	0.036 (2)	0.085 (3)	0.023 (2)	0.000 (3)	0.019 (2)
O2B1	0.061 (3)	0.057 (3)	0.076 (3)	0.032 (2)	−0.005 (3)	0.024 (2)
C1B1	0.047 (4)	0.040 (3)	0.050 (3)	0.022 (3)	0.015 (3)	0.024 (3)
C2B1	0.042 (3)	0.037 (3)	0.044 (3)	0.020 (3)	0.013 (3)	0.015 (3)
N1B1	0.055 (3)	0.037 (3)	0.046 (3)	0.026 (2)	0.015 (2)	0.016 (2)
C3B1	0.041 (3)	0.035 (3)	0.050 (3)	0.016 (3)	0.012 (3)	0.019 (3)
C4B1	0.060 (4)	0.096 (6)	0.059 (4)	0.048 (4)	0.014 (4)	0.029 (4)
C5B1	0.098 (6)	0.125 (8)	0.052 (5)	0.067 (6)	0.009 (5)	0.030 (5)
C6B1	0.123 (8)	0.074 (5)	0.043 (4)	0.047 (5)	0.017 (5)	0.020 (4)
C7B1	0.103 (7)	0.121 (7)	0.070 (5)	0.071 (6)	0.051 (5)	0.041 (5)
C8B1	0.066 (4)	0.097 (6)	0.057 (4)	0.050 (4)	0.025 (4)	0.030 (4)
O1B2	0.108 (4)	0.063 (3)	0.090 (4)	0.059 (3)	0.046 (3)	0.041 (3)
O2B2	0.055 (3)	0.056 (3)	0.076 (3)	0.024 (2)	0.025 (2)	0.041 (2)
C1B2	0.052 (4)	0.045 (3)	0.049 (3)	0.028 (3)	0.011 (3)	0.023 (3)
C2B2	0.053 (3)	0.040 (3)	0.047 (3)	0.027 (3)	0.019 (3)	0.022 (3)
N1B2	0.058 (3)	0.043 (3)	0.053 (3)	0.030 (3)	0.018 (3)	0.024 (2)
C3B2	0.057 (4)	0.045 (3)	0.044 (3)	0.029 (3)	0.017 (3)	0.025 (3)
C4B2	0.074 (5)	0.090 (5)	0.065 (5)	0.045 (4)	0.036 (4)	0.047 (4)
C5B2	0.107 (7)	0.123 (8)	0.068 (5)	0.060 (7)	0.047 (5)	0.053 (5)
C6B2	0.108 (7)	0.079 (6)	0.046 (4)	0.038 (5)	0.009 (5)	0.024 (4)
C7B2	0.086 (6)	0.082 (6)	0.056 (5)	0.024 (5)	−0.009 (4)	0.025 (4)
C8B2	0.062 (5)	0.078 (5)	0.052 (4)	0.019 (4)	0.014 (4)	0.035 (4)

Geometric parameters (Å, º) top

S1A1—O1A1	1.426 (4)	C3B1—C8B1	1.374 (8)
S1A1—O2A1	1.439 (4)	C4B1—H4B1	0.9300
S1A1—O3A1	1.409 (5)	C4B1—C5B1	1.359 (10)
S1A1—C1A1	1.791 (7)	C5B1—H5B1	0.9300
C1A1—F1A1	1.285 (8)	C5B1—C6B1	1.347 (11)
C1A1—F2A1	1.326 (8)	C6B1—H6B1	0.9300
C1A1—F3A1	1.276 (8)	C6B1—C7B1	1.376 (11)
S1A2—O1A2	1.421 (4)	C7B1—H7B1	0.9300
S1A2—O2A2	1.412 (5)	C7B1—C8B1	1.377 (10)
S1A2—O3A2	1.419 (5)	C8B1—H8B1	0.9300
S1A2—O1X2	1.52 (7)	O1B2—H1B2	0.8200
S1A2—O2X2	1.26 (6)	O1B2—C1B2	1.318 (7)
S1A2—O3X2	1.54 (6)	O2B2—C1B2	1.191 (7)
S1A2—C1A2	1.800 (7)	C1B2—C2B2	1.509 (7)
C1A2—F1A2	1.310 (8)	C2B2—H2B2	0.9800
C1A2—F2A2	1.297 (8)	C2B2—N1B2	1.476 (7)
C1A2—F3A2	1.301 (7)	C2B2—C3B2	1.505 (7)
C1A2—F1X2	1.36 (5)	N1B2—H1BD	0.8900
C1A2—F2X2	1.27 (5)	N1B2—H1BE	0.8900
C1A2—F3X2	1.25 (6)	N1B2—H1BF	0.8900
O1B1—H1B1	0.8200	C3B2—C4B2	1.373 (8)
O1B1—C1B1	1.312 (7)	C3B2—C8B2	1.367 (9)
O2B1—C1B1	1.197 (7)	C4B2—H4B2	0.9300
C1B1—C2B1	1.501 (7)	C4B2—C5B2	1.393 (10)
C2B1—H2B1	0.9800	C5B2—H5B2	0.9300
C2B1—N1B1	1.498 (7)	C5B2—C6B2	1.343 (12)
C2B1—C3B1	1.497 (7)	C6B2—H6B2	0.9300
N1B1—H1BA	0.8900	C6B2—C7B2	1.353 (11)
N1B1—H1BB	0.8900	C7B2—H7B2	0.9300
N1B1—H1BC	0.8900	C7B2—C8B2	1.364 (9)
C3B1—C4B1	1.369 (8)	C8B2—H8B2	0.9300

O1A1—S1A1—O2A1	114.5 (3)	C4B1—C3B1—C2B1	120.7 (5)
O1A1—S1A1—C1A1	105.5 (3)	C4B1—C3B1—C8B1	118.1 (6)
O2A1—S1A1—C1A1	104.5 (3)	C8B1—C3B1—C2B1	121.1 (5)
O3A1—S1A1—O1A1	111.9 (3)	C3B1—C4B1—H4B1	118.7
O3A1—S1A1—O2A1	115.4 (3)	C5B1—C4B1—C3B1	122.6 (7)
O3A1—S1A1—C1A1	103.5 (3)	C5B1—C4B1—H4B1	118.7
F1A1—C1A1—S1A1	112.2 (6)	C4B1—C5B1—H5B1	120.4
F1A1—C1A1—F2A1	103.2 (7)	C6B1—C5B1—C4B1	119.1 (7)
F2A1—C1A1—S1A1	110.9 (5)	C6B1—C5B1—H5B1	120.4
F3A1—C1A1—S1A1	114.3 (5)	C5B1—C6B1—H6B1	119.9
F3A1—C1A1—F1A1	108.3 (7)	C5B1—C6B1—C7B1	120.2 (7)
F3A1—C1A1—F2A1	107.3 (7)	C7B1—C6B1—H6B1	119.9
O1A2—S1A2—C1A2	103.2 (3)	C6B1—C7B1—H7B1	119.8
O2A2—S1A2—O1A2	113.8 (3)	C6B1—C7B1—C8B1	120.3 (7)
O2A2—S1A2—O3A2	117.2 (4)	C8B1—C7B1—H7B1	119.8
O2A2—S1A2—C1A2	103.5 (3)	C3B1—C8B1—C7B1	119.7 (7)
O3A2—S1A2—O1A2	113.0 (3)	C3B1—C8B1—H8B1	120.2
O3A2—S1A2—C1A2	103.9 (3)	C7B1—C8B1—H8B1	120.2
O1X2—S1A2—O3X2	105 (4)	C1B2—O1B2—H1B2	109.5
O1X2—S1A2—C1A2	98 (3)	O1B2—C1B2—C2B2	109.9 (5)
O2X2—S1A2—O1X2	114 (4)	O2B2—C1B2—O1B2	125.5 (5)
O2X2—S1A2—O3X2	103 (4)	O2B2—C1B2—C2B2	124.5 (5)
O2X2—S1A2—C1A2	119 (3)	C1B2—C2B2—H2B2	108.6
O3X2—S1A2—C1A2	117 (2)	N1B2—C2B2—C1B2	108.1 (4)
F1A2—C1A2—S1A2	111.9 (5)	N1B2—C2B2—H2B2	108.6
F2A2—C1A2—S1A2	113.8 (5)	N1B2—C2B2—C3B2	112.5 (4)
F2A2—C1A2—F1A2	105.5 (6)	C3B2—C2B2—C1B2	110.3 (5)
F2A2—C1A2—F3A2	107.0 (6)	C3B2—C2B2—H2B2	108.6
F3A2—C1A2—S1A2	112.1 (5)	C2B2—N1B2—H1BD	109.5
F3A2—C1A2—F1A2	106.1 (7)	C2B2—N1B2—H1BE	109.5
F1X2—C1A2—S1A2	109 (2)	C2B2—N1B2—H1BF	109.5
F2X2—C1A2—S1A2	121 (2)	H1BD—N1B2—H1BE	109.5
F2X2—C1A2—F1X2	115 (3)	H1BD—N1B2—H1BF	109.5
F3X2—C1A2—S1A2	101 (3)	H1BE—N1B2—H1BF	109.5
F3X2—C1A2—F1X2	107 (4)	C4B2—C3B2—C2B2	119.0 (6)
F3X2—C1A2—F2X2	102 (4)	C8B2—C3B2—C2B2	121.9 (5)
C1B1—O1B1—H1B1	109.5	C8B2—C3B2—C4B2	119.0 (6)
O1B1—C1B1—C2B1	112.3 (5)	C3B2—C4B2—H4B2	120.6
O2B1—C1B1—O1B1	123.9 (5)	C3B2—C4B2—C5B2	118.7 (7)
O2B1—C1B1—C2B1	123.7 (5)	C5B2—C4B2—H4B2	120.6
C1B1—C2B1—H2B1	108.4	C4B2—C5B2—H5B2	119.2
N1B1—C2B1—C1B1	107.5 (5)	C6B2—C5B2—C4B2	121.5 (7)
N1B1—C2B1—H2B1	108.4	C6B2—C5B2—H5B2	119.2
C3B1—C2B1—C1B1	113.1 (5)	C5B2—C6B2—H6B2	120.4
C3B1—C2B1—H2B1	108.4	C5B2—C6B2—C7B2	119.1 (7)
C3B1—C2B1—N1B1	110.8 (4)	C7B2—C6B2—H6B2	120.4
C2B1—N1B1—H1BA	109.5	C6B2—C7B2—H7B2	119.5
C2B1—N1B1—H1BB	109.5	C6B2—C7B2—C8B2	120.9 (8)
C2B1—N1B1—H1BC	109.5	C8B2—C7B2—H7B2	119.5
H1BA—N1B1—H1BB	109.5	C3B2—C8B2—H8B2	119.7
H1BA—N1B1—H1BC	109.5	C7B2—C8B2—C3B2	120.7 (7)
H1BB—N1B1—H1BC	109.5	C7B2—C8B2—H8B2	119.7

O1A1—S1A1—C1A1—F1A1	176.1 (6)	O2B1—C1B1—C2B1—C3B1	113.8 (7)
O1A1—S1A1—C1A1—F2A1	61.3 (6)	C1B1—C2B1—C3B1—C4B1	139.3 (6)
O1A1—S1A1—C1A1—F3A1	−60.1 (7)	C1B1—C2B1—C3B1—C8B1	−44.0 (8)
O2A1—S1A1—C1A1—F1A1	54.9 (6)	C2B1—C3B1—C4B1—C5B1	178.4 (7)
O2A1—S1A1—C1A1—F2A1	−59.8 (6)	C2B1—C3B1—C8B1—C7B1	−179.1 (7)
O2A1—S1A1—C1A1—F3A1	178.8 (6)	N1B1—C2B1—C3B1—C4B1	−99.9 (6)
O3A1—S1A1—C1A1—F1A1	−66.2 (7)	N1B1—C2B1—C3B1—C8B1	76.9 (7)
O3A1—S1A1—C1A1—F2A1	179.0 (6)	C3B1—C4B1—C5B1—C6B1	−0.6 (13)
O3A1—S1A1—C1A1—F3A1	57.6 (7)	C4B1—C3B1—C8B1—C7B1	−2.2 (10)
O1A2—S1A2—C1A2—F1A2	61.5 (6)	C4B1—C5B1—C6B1—C7B1	0.3 (13)
O1A2—S1A2—C1A2—F2A2	−57.9 (6)	C5B1—C6B1—C7B1—C8B1	−1.1 (13)
O1A2—S1A2—C1A2—F3A2	−179.5 (6)	C6B1—C7B1—C8B1—C3B1	2.1 (12)
O2A2—S1A2—C1A2—F1A2	−179.6 (6)	C8B1—C3B1—C4B1—C5B1	1.5 (11)
O2A2—S1A2—C1A2—F2A2	61.0 (7)	O1B2—C1B2—C2B2—N1B2	−162.1 (5)
O2A2—S1A2—C1A2—F3A2	−60.6 (7)	O1B2—C1B2—C2B2—C3B2	74.5 (6)
O3A2—S1A2—C1A2—F1A2	−56.6 (6)	O2B2—C1B2—C2B2—N1B2	18.7 (8)
O3A2—S1A2—C1A2—F2A2	−176.0 (6)	O2B2—C1B2—C2B2—C3B2	−104.7 (7)
O3A2—S1A2—C1A2—F3A2	62.4 (6)	C1B2—C2B2—C3B2—C4B2	−128.9 (6)
O1X2—S1A2—C1A2—F1X2	57 (4)	C1B2—C2B2—C3B2—C8B2	49.5 (8)
O1X2—S1A2—C1A2—F2X2	−79 (4)	C2B2—C3B2—C4B2—C5B2	178.3 (6)
O1X2—S1A2—C1A2—F3X2	170 (4)	C2B2—C3B2—C8B2—C7B2	−177.6 (6)
O2X2—S1A2—C1A2—F1X2	−179 (4)	N1B2—C2B2—C3B2—C4B2	110.3 (6)
O2X2—S1A2—C1A2—F2X2	45 (5)	N1B2—C2B2—C3B2—C8B2	−71.2 (7)
O2X2—S1A2—C1A2—F3X2	−66 (5)	C3B2—C4B2—C5B2—C6B2	−1.0 (13)
O3X2—S1A2—C1A2—F1X2	−54 (4)	C4B2—C3B2—C8B2—C7B2	0.9 (11)
O3X2—S1A2—C1A2—F2X2	170 (4)	C4B2—C5B2—C6B2—C7B2	1.4 (14)
O3X2—S1A2—C1A2—F3X2	58 (4)	C5B2—C6B2—C7B2—C8B2	−0.7 (14)
O1B1—C1B1—C2B1—N1B1	170.0 (5)	C6B2—C7B2—C8B2—C3B2	−0.5 (12)
O1B1—C1B1—C2B1—C3B1	−67.3 (6)	C8B2—C3B2—C4B2—C5B2	−0.2 (10)
O2B1—C1B1—C2B1—N1B1	−8.9 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1B1—H1B1···O2A1	0.82	1.96	2.735 (6)	159
N1B1—H1BA···O1A1ⁱ	0.89	2.12	2.865 (6)	141
N1B1—H1BB···O1A1ⁱⁱ	0.89	2.14	2.973 (6)	155
N1B1—H1BC···O2B2ⁱⁱ	0.89	2.12	2.960 (6)	157
O1B2—H1B2···O2A2ⁱⁱⁱ	0.82	1.85	2.614 (6)	155
N1B2—H1BD···O3A2^iv	0.89	2.11	2.842 (7)	139
N1B2—H1BE···O3A1	0.89	2.01	2.883 (7)	168
N1B2—H1BF···O1A2	0.89	1.99	2.878 (6)	173

Symmetry codes: (i) −x, −y+1, −z+2; (ii) x, y+1, z; (iii) x, y−1, z; (iv) −x+1, −y+1, −z+2.

Table 1 Thermodynamic parameters (T_onset, T_max, ΔH_onset and ΔS_onset) for dehydration and melting processes estimated from DSC measurements top

Process	T_onset^a (K)	T_max^a (K)	ΔH_onset^a (kJ mol^-1)	ΔS_onset^a (J mol^-1 K^-1)
Dehydration	/353.4	/379.2	/21.8	/61.7
Solid→liquid (1st cycle)	456.3/461.3	448.7/493.5	-20.6/56.2	-45.2/121.8
Solid→liquid (2nd cycle)	450.6/497.1	444.0/503.6	-20.1/26.2	-44.5/52.7

Note: (a) the values given before and after `/' are related to the cooling and heating process, respectively.

Table 3 The wavenumbers (cm^-1), IR and Raman intensities of the bands observed in the vibrational spectra of polycrystalline samples of the PGTFH and PGTF (after annealing) at room temperature top

PGTFH	PGTF	Proposed assignments^b,c
IR (cm^-1)	Raman^a (cm^-1)	IR (cm^-1)	Raman^a (cm^-1)
3418 s sh				ν_asH₂O(cryst)
3361 s b				ν_asH₂O(cryst)
3228 s	3214 (2)		3214 (2)	νN—H···O
3164 s	3165 (2)	3191 s sh		νN—H···O
		3160 vs b		νOH (O—H···O)
3147 s sh		3153 s b	3150 (3)	νN—H···O/ν_8a(νCC) + ν_19a(νCC)
3111 w				ν_8b(νCC) + ν_19a(νCC)
3103 w		3098 s sh
		3084 s sh	3084 (10)
	3079 (15)		3074 (8)
	3061 (8)	3067 s sh	3066 (13)	ν₂(νCH)
	3051 (4)	3054 s sh	3055 (7)	ν_20b(νCH)
3046 vs b				νOH (A) (O—H···O_w)
3042 s	3042 (3)	3041 s sh		ν_7a(νCH)
	3024 (3)			ν_20a(νCH)
	3019 (3)		3020 (3)	ν_7b(νCH)
			3002 (5)
	2991 (2)		2996 (4)
2968 s	2970 (6)	2975 s sh	2980 (6)	νCH/2 × ν_19a(CC)
			2974 (5) sh
2933 w sh
2869 m		2852 w sh
2776 w
2728 vw		2723 w
2697 vw sh
2672 w
2623 m b		2624 w b		νOH (B) (O—H···O_w)
2602 m		2607 w b
2528 vw
		1764 sh	1763 (10) sh	νC═O
		1742 s	1748 (19)	νC═O
1722 s	1726 (7)			νC═O
1652 w b				δH₂O
1614 m	1606 (22)	1603 m	1605 (33)	ν_8a(νCC)
1591	1591 (16)		1590 (27)	ν_8b(νCC)
1582 w				δ_asNH₃⁺
		1508 s sh		ν_19a(νCC)
1501 s	1502 (2)	1503 s	1502 (14)	ν_19a(νCC)
1460 s	1462 (2)	1460 m	1462 (15)	ν_19b(νCC) + ν₁₄(νCC)
1456 w sh				δOH (O—H···O_w)
		1420 w	1423 (15)	δ_sNH₃⁺
1399 vw				νC-O(H)
1358 w	1357 (3)	1356 m	1357 (17)	δCH
1347 s	1344 (2)	1341 w		γCH + νNH₃⁺
1307 vw sh	1308 (2)		1305 (17)	ν₃(νCH)
		1284 vs	1284 (18)
1277 vs		1278 vs sh	1270 (19)	ν_asSO₃
1266 vs	1268 (9)	1249 s	1251 (19)	ν_asSO₃
1237 vs				νC—O(H)
1227 vs	1228 (14)	1227 vs b	1229 (30)	ν_sCF₃/νC—O(H)
		1220 vs sh	1213 (22)
1194 w	1196 (19)	1200 w sh	1192 (29)	ν(C—C_ring) + νCH + νCN
1182 s	1184 (6) sh	1176 vs		ν_9a(δCH)
1175 s	1174 (6)	1176 vs sh	1172 (19)	ν_asCF₃
1159 w	1160 (10)	1158 s	1158 (23)	ν₁₅(νCH)
1128 w	1127 (2)			δOH (O—H···O_w)
1111 vw	1111 (3)	1111 m	1111 (18)	ν_asSO₃
1100 w	1099 (3)	1097 m	1097 (17)	νCN + ν_18b(δCH)/γCH
1074 w	1073 (2)	1071 m	1071 (17)	ν_18b(δCH) + νCN
1031 vs	1037 (56)	1034 vs	1039 (85)	ν_sSO₃
	1021 (18)	1027	1017 (24)	ν_18a(δCH)
	1003 (100)	1008 vw	1003 (100)	ν₁₂(δCC) + ν₁(νCC)
991 vw	992 (5)	988 vw	992 (21) sh	ν₅(νCH)
	970 (2)	963 vw		ν_17a(νCH)
952 m b				γOH (O—H···O_w)
922 w	920 (3)	921 m	923 (17)	ν_17b(νCH)
888 m	889 (4)	882 m	882 (19)	ν₁(νCC)
		849 vw
833 w	833 (11)	827 m	825 (26)	2 × ν_16a(δCC)
		795 w b		γOH (O—H···O)
766 s	766 (38)	766 w sh	767 (52)	δ_sCF₃
		761 m		δ_sCF₃
		744 vw
737 m	741 (9)		727 (29)	ν₁₁(νCH) + νCOO + ν₄(νCC)
697 s		695 m		νCCN + νCOO
672 vw				τH₂O, ρH₂O
			657 (17)
643 s	652 (3)	643 s	646 (17)	δ_sSO₃
	635 (3)	637 s sh		δCOO
615 m	616 (14)	616 vw	616 (30)	ν(C_ring—CN) + ν_6b(νCC)/ν_6a(νCC)
597 vw				ωH₂O
583 sh	585 (9)	585 m	584 (23)	δ_sSO₃
573 s	577 (9)	574 m sh	575 (20)	δ_asCF₃
522 m		525 w	527 (16)	ν_16b(νCC) +ν(CCC)_ringC
514 s	513 (5) b	512 m	514 (17)	δ_asSO₃
		498 m	497 (21)	tNH₃⁺(dehydrated)
485 w	484 (4)	477 w	479 (19)	δCC═O + νCC/skeletal vibrations
	352 (25) sh		352 (36) sh	ρSO₃
	349 (27)		348 (39)	ρSO₃
	318 (22)		322 (40)	νCS
	284 (4)		270 (16)	ν_r(NH₃⁺)
			222 (12)

Notes: (a) relative intensities are given in parentheses with respect to the most intense Raman band in the PGTFH and in the PGTF crystals spectra at 1003 cm^-1, respectively. Their intensities were taken as 100. (b) Used symbols: vs = very strong, s = strong, m = medium, w = weak, vw = very weak, b = broad, sh = shoulder; ν = stretching (s = symmetric and as = asymmetric), δ = bending in plane, γ = bending out of plane, ρ = rocking, τ = torsion, ω = wagging and t = twisting. (c) The phenyl-ring internal vibrations are marked by symbols taken from Varsányi (1969) and Wojtkowiak & Chabanel (1977).

Table 3 Analysis of the fundamental (k = 0) modes of the PGTF crystal top

C_i^a	N^b	A	T	L	C₆H₅CHNH₃COOH	CF₃SO₃^-	Selection rules
					ν_PG	ν_H	ν_ac	IR	Raman
A_g	174	0	12	12	108	6	36	ia	xx,yy,zz,xy,xz,yz
A_u	174	3	9	12	108	6	36	x,y,z	ia

Notes: (a) unit-cell symmetry; (b) abbreviations: N is the total number of modes, A are the acoustic modes, T are the translation modes, L are the libration modes; ν_PG are the internal vibrations of phenylglycine, ν_H are the modes of the proton in O—H···O hydrogen bonds and ν_ac are the internal modes of the trifluoromethanesulfonate anion.

Table 2 Analysis of the fundamental (k = 0) modes of the PGTFH crystal top

C₂_h^a	N^b	A	T	L	C₆H₅CHNH₃COOH	CF₃SO₃^-	H₂O	Selection rules
					ν_PG	ν_H	ν_ac	ν_w	IR	Raman
A_g	96	0	9	9	54	3	18	3	ia	xx,yy,zz,xy
B_g	96	0	9	9	54	3	18	3	ia	xz,yz
A_u	96	1	8	9	54	3	18	3	z	ia
B_u	96	2	7	9	54	3	18	3	x,y	ia

Notes: (a) unit-cell symmetry; (b) abbreviations: N is the total number of modes, A are the acoustic modes, T are the translation modes, L are the libration modes; ν_PG are the internal vibrations of phenylglycine, ν_H are the modes of the proton in O—H···O hydrogen bonds, ν_ac are the internal modes of the trifluoromethanesulfonate anion and ν_w are the internal vibrations of water molecules.

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The dehydration process in the DL-phenyl­glycinium tri­fluoro­methane­sulfonate monohydrate crystal revealed by XRD, vibrational and DSC studies

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The dehydration process in the DL-phenylglycinium trifluoromethanesulfonate monohydrate crystal revealed by XRD, vibrational and DSC studies